JP5509525B2 - Method for producing polymer fine particles - Google Patents
Method for producing polymer fine particles Download PDFInfo
- Publication number
- JP5509525B2 JP5509525B2 JP2008022278A JP2008022278A JP5509525B2 JP 5509525 B2 JP5509525 B2 JP 5509525B2 JP 2008022278 A JP2008022278 A JP 2008022278A JP 2008022278 A JP2008022278 A JP 2008022278A JP 5509525 B2 JP5509525 B2 JP 5509525B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- polymer fine
- water
- polymerization
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 117
- 239000010419 fine particle Substances 0.000 title claims description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 239000000178 monomer Substances 0.000 claims description 108
- 239000002245 particle Substances 0.000 claims description 96
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 73
- 229920002554 vinyl polymer Polymers 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 48
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 40
- 239000007800 oxidant agent Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 23
- 239000003381 stabilizer Substances 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 12
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012071 phase Substances 0.000 description 53
- 238000006116 polymerization reaction Methods 0.000 description 50
- 239000000203 mixture Substances 0.000 description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 29
- 238000003756 stirring Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- -1 N, N-dimethylaminoethyl Chemical group 0.000 description 18
- 238000005259 measurement Methods 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 229920006037 cross link polymer Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000001593 sorbitan monooleate Substances 0.000 description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 description 4
- 229940035049 sorbitan monooleate Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000490 cosmetic additive Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007717 redox polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- BZGMEGUFFDTCNP-UHFFFAOYSA-N 2-hydroperoxy-2-methylpentane Chemical compound CCCC(C)(C)OO BZGMEGUFFDTCNP-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- KUDZDPMCQYHSSJ-UHFFFAOYSA-N 2-pentylidenebutanedioic acid Chemical compound CCCCC=C(C(O)=O)CC(O)=O KUDZDPMCQYHSSJ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- WOAMRAPSJUZQJV-UHFFFAOYSA-N 3-oxopent-4-ene-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)C(=O)C=C WOAMRAPSJUZQJV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RHSCFNJCBGIZAS-UHFFFAOYSA-N CC(=C)C(=O)OCCCOP(=O)=O Chemical compound CC(=C)C(=O)OCCCOP(=O)=O RHSCFNJCBGIZAS-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Description
本発明は、重合体微粒子の製造方法に関する。より詳細には、本発明は、ビニル系単量体の逆相懸濁重合によって、粒径の揃った、特定範囲の粒径を有する高品質の重合体微粒子を、粒子同士の凝集などを生ずることなく、スケールアップしても安定した状態で生産性良く製造する方法に関する。 The present invention relates to a method for producing polymer fine particles. More specifically, in the present invention, high-quality polymer fine particles having a uniform particle size and having a particle size in a specific range are produced by aggregation of particles by reverse phase suspension polymerization of a vinyl monomer. The present invention relates to a method for producing a product in a stable state with good productivity even when scaled up.
ミクロンサイズの球状重合体微粒子は、化粧品添加剤、各種化学物質の担持体、スペーサー、クロマトグラフィー用のカラム充填剤、光拡散剤、多孔質化剤、軽量化剤、ブロッキング防止剤、記録紙用表面改質剤などに利用されている。
その中でも、親水性の架橋重合体微粒子は、含水ゲル微粒子として利用でき、化粧品添加剤、担持体、多孔質化剤、軽量化剤、記録紙用表面改質剤として有用である。
Micron-sized spherical polymer fine particles are used for cosmetic additives, various chemical substances, spacers, column fillers for chromatography, light diffusing agents, porosifying agents, lightening agents, anti-blocking agents, and recording paper. It is used as a surface modifier.
Among these, hydrophilic crosslinked polymer fine particles can be used as hydrogel fine particles, and are useful as cosmetic additives, carriers, porogens, lightening agents, and surface modifiers for recording paper.
ビニル系単量体の逆相懸濁重合によって重合体粒子を製造することは従来から行われており、逆相懸濁重合によって親水性の架橋重合体粒子を製造する従来技術としては、分散剤として特定のＨＬＢを有する化合物を用い、重合前にモノマーの油中水型微小分散滴を形成しておき、これを滴下しつつ重合させる方法（特許文献１）、吸水性ポリマー粒子、油溶性重合開始剤及び分散剤の存在下、逆相懸濁重合させ、重合中又は重合後に、疎水性ビニルモノマー及び油溶性重合開始剤を添加し重合させる方法（特許文献２）、親水性ビニルモノマーを、1種以上の官能基を有するシリコーン化合物を反応系に存在させ、逆相懸濁重合させる方法（特許文献３）などが知られている。
しかしながら、これらの従来技術による場合は、重合時や重合後の重合体粒子の分散安定性が不十分であったり、得られる重合体粒子の粒径が不揃いであったり、得られる重合体粒子の親水性が低下するなどの問題があった。特に、多官能ビニル系単量体の使用割合を多くして、架橋度の高い親水性架橋重合体粒子を逆相懸濁重合で製造する場合には、重合安定性の低下が大きく、粒子の凝集、得られる重合体粒子の品質低下、生産性の低下などの問題が生じ易いものであった。
上記いずれの製造方法も７０℃以上の高温にした反応器に単量体乳化液を１時間以上かけて連続的に供給して重合させる方法であるため、粒子間の凝集などが生じやすく、得られる重合体粒子の粒径が不揃いとなり、また、多官能ビニル系単量体などの架橋剤を多く使用した場合には、未反応の架橋剤の大部分が連続相側に溶出しやすくなり、その状態で重合を続けることにより粒子が凝集し、上記のような重合体粒子の品質低下につながると考えられる。
Production of polymer particles by reverse-phase suspension polymerization of vinyl monomers has been conventionally performed. Conventional techniques for producing hydrophilic crosslinked polymer particles by reverse-phase suspension polymerization include dispersing agents. As a method, a water-in-oil microdispersion droplet of a monomer is formed before polymerization using a compound having a specific HLB, and the polymerization is performed while dropping the monomer (Patent Document 1), water-absorbing polymer particles, oil-soluble polymerization In the presence of an initiator and a dispersant, reverse phase suspension polymerization is performed, and during or after polymerization, a method of adding a hydrophobic vinyl monomer and an oil-soluble polymerization initiator to polymerize (Patent Document 2), a hydrophilic vinyl monomer, A method (Patent Document 3) in which a silicone compound having one or more functional groups is present in a reaction system and subjected to reverse phase suspension polymerization is known.
However, in the case of these conventional techniques, the dispersion stability of the polymer particles after polymerization or after polymerization is insufficient, the particle diameters of the obtained polymer particles are uneven, or the polymer particles obtained There were problems such as a decrease in hydrophilicity. In particular, when hydrophilic cross-linked polymer particles having a high degree of cross-linking are produced by reverse phase suspension polymerization by increasing the use ratio of the polyfunctional vinyl-based monomer, the polymerization stability is greatly reduced. Problems such as agglomeration, deterioration of the quality of the resulting polymer particles, and productivity are likely to occur.
Any of the above production methods is a method in which a monomer emulsion is continuously supplied to a reactor heated to a high temperature of 70 ° C. or higher for polymerization for 1 hour or more, and therefore, aggregation between particles is likely to occur. The particle size of the resulting polymer particles is uneven, and when a large amount of cross-linking agent such as a polyfunctional vinyl monomer is used, most of the unreacted cross-linking agent tends to elute to the continuous phase side, By continuing polymerization in this state, it is considered that the particles aggregate and lead to a deterioration in the quality of the polymer particles as described above.
さらに、特定な吸水量を有する吸水性ポリマーの製造において、逆相懸濁重合による吸水性ポリマー粒子をレドックス重合開始剤を用いて製造する例示があり、油溶性酸化剤であるｔ−ブチルヒドロキシパーオキシドを供給した後に水溶性還元剤である重亜硫酸ナトリウムを供給して重合体微粒子を製造することが記載されている（特許文献４）
この製造方法によれば、前記従来技術に比べて微粒子の粒径制御は精密に行うことが出来る。しかしながら、水溶性還元剤が十分に拡散しない段階で重合反応が起こるため、粒径の揃った、特定範囲の粒径を有する高品質の重合体微粒子を、粒子同士の凝集などを生ずることなく、安定した状態で生産性良く製造する方法としては満足するものではない。
Furthermore, in the production of a water-absorbing polymer having a specific water absorption amount, there is an example in which water-absorbing polymer particles by reverse phase suspension polymerization are produced using a redox polymerization initiator, and t-butyl hydroxypar which is an oil-soluble oxidant. It is described that polymer fine particles are produced by supplying sodium bisulfite which is a water-soluble reducing agent after supplying oxide (Patent Document 4).
According to this manufacturing method, the particle size of fine particles can be controlled more precisely than in the prior art. However, since the polymerization reaction occurs in a stage where the water-soluble reducing agent does not sufficiently diffuse, high-quality polymer fine particles having a uniform particle size and having a specific range of particle size can be produced without causing aggregation of particles, It is not satisfactory as a method for producing in a stable state with good productivity.
本発明の目的は、逆相懸濁重合によって、粒径の揃った数μｍ〜数十μｍオーダーの粒子径を有する高品質の重合体微粒子を、粒子同士の凝集などを生ずることなく、良好な分散安定性を維持しながら、生産性良く製造する方法を提供することである。
特に、本発明は、架橋度の高い親水性架橋重合体微粒子を製造する場合であっても、高い重合安定性で、懸濁安定性を維持しながら、粒径の揃った高品質の重合体微粒子を、生産性よく、円滑に製造することのできる逆相懸濁重合方法を提供することである。
The object of the present invention is to produce high-quality polymer fine particles having a particle size on the order of several μm to several tens of μm with a uniform particle size by reverse-phase suspension polymerization without causing aggregation of the particles. The object is to provide a method for producing with good productivity while maintaining dispersion stability.
In particular, the present invention provides a high-quality polymer having a uniform particle size while maintaining suspension stability with high polymerization stability even when producing hydrophilic crosslinked polymer fine particles having a high degree of crosslinking. An object of the present invention is to provide a reverse phase suspension polymerization method capable of producing fine particles smoothly with good productivity.
本発明者らは、前記した目的を達成するために鋭意検討を重ねてきた。特に、ビニル系単量体を逆相懸濁重合させて重合体微粒子を製造するに際し、従来技術に比べて低温で、かつ短時間で重合を行うことが重要と考え、その条件を検討した結果、重合開始剤として油溶性酸化剤と水溶性還元剤を使用し、かつ、水溶性還元剤を供給した後に油溶性酸化剤を供給した逆相懸濁重合を行うと、数μｍ〜数十μｍオーダーの粒径を有し、しかも粒径の揃った、高品質の球状の重合体微粒子を、重合時や重合後に重合体粒子の凝集、塊化、重合装置への付着などを生ずることなく、良好な分散安定性、重合安定性を維持しながら、生産性良く製造できることを見出した。 The present inventors have intensively studied to achieve the above-described object. In particular, when producing polymer fine particles by reverse-phase suspension polymerization of vinyl monomers, it is important to perform polymerization at a low temperature and in a short time compared to conventional techniques, and the results of studying the conditions When reverse-phase suspension polymerization is performed using an oil-soluble oxidizing agent and a water-soluble reducing agent as a polymerization initiator and supplying an oil-soluble oxidizing agent after supplying the water-soluble reducing agent, several μm to several tens of μm High-quality spherical polymer particles having a particle size of the order and uniform particle size, without causing aggregation or agglomeration of the polymer particles during polymerization or after polymerization, adhesion to the polymerization apparatus, etc. It has been found that it can be produced with good productivity while maintaining good dispersion stability and polymerization stability.
すなわち、上記課題を解決するための本発明は、以下に記載するものである。
第１発明は、ビニル系単量体を逆相懸濁重合させて重合体微粒子を製造する方法であって、重合開始剤として油溶性酸化剤と水溶性還元剤を使用し、かつ、水溶性還元剤を供給した後に油溶性酸化剤を供給することを特徴とする重合体微粒子の製造方法である。
第２発明は、上記ビニル系単量体が（メタ）アクリル酸、（メタ）アクリルアミドおよび２−アクリルアミド−２−メチルプロパンスルホン酸の１種又は２種以上を含むものである上記第１発明に記載の重合体微粒子の製造方法である。
第３発明は、油溶性酸化剤の全量を２０秒〜１２０秒の時間をかけて供給する上記第１発明または第２発明に記載の重合体微粒子の製造方法である。
第４発明は、油溶性酸化剤を反応液の液面より下部に位置する供給口から反応器に供給する上記第１発明〜第３発明のいずれかに記載の重合体微粒子の製造方法である。
第５発明は、ビニル系単量体由来の重合体の末端にラジカル重合性不飽和基を有するマクロモノマーを分散安定剤として用いる上記第１発明〜第４発明のいずれかに記載の重合体微粒子の製造方法である。
第６発明は、逆相懸濁重合により製造される重合体微粒子が、０．５ｍｏｌ％以上の架橋密度を有する重合体微粒子である上記第１発明〜第５発明のいずれかに記載の重合体微粒子の製造方法である。
That is, this invention for solving the said subject is described below.
The first invention is a method for producing polymer fine particles by subjecting a vinyl monomer to reverse phase suspension polymerization, using an oil-soluble oxidizing agent and a water-soluble reducing agent as a polymerization initiator, and water-soluble A method for producing polymer fine particles, wherein an oil-soluble oxidant is supplied after a reducing agent is supplied.
According to a second invention, in the first invention, the vinyl monomer contains one or more of (meth) acrylic acid, (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid. This is a method for producing polymer fine particles.
A third invention is the method for producing polymer fine particles according to the first invention or the second invention , wherein the total amount of the oil-soluble oxidant is supplied over a period of 20 seconds to 120 seconds.
A fourth invention is the method for producing polymer fine particles according to any one of the first to third inventions , wherein the oil-soluble oxidant is supplied to the reactor from a supply port located below the surface of the reaction solution. .
The fifth invention is the polymer fine particle according to any one of the first to fourth inventions, wherein a macromonomer having a radical polymerizable unsaturated group at a terminal of the polymer derived from the vinyl monomer is used as a dispersion stabilizer. It is a manufacturing method.
A sixth invention is the polymer according to any one of the first to fifth inventions, wherein the polymer fine particles produced by reversed-phase suspension polymerization are polymer fine particles having a crosslinking density of 0.5 mol% or more. This is a method for producing fine particles.
第７発明は、逆相懸濁重合により製造される重合体微粒子が、水による飽和膨潤状態における平均粒子径が１００μｍ以下であり、かつ水による飽和膨潤状態において１５０μｍ以上の粒径を示す粒子の割合が１．０質量％以下の重合体微粒子である上記第１発明〜第６発明のいずれかに記載の重合体微粒子の製造方法である。
第８発明は、逆相懸濁重合により製造される重合体微粒子が、５〜５０倍の吸水倍率を有し、水による飽和膨潤状態での平均粒子径が５〜７０μｍであり、かつ水による飽和膨潤状態において１５０μｍ以上の粒径を示す粒子の割合が０．３質量％以下の重合体微粒子である上記第１発明〜第６発明のいずれかに記載の重合体微粒子の製造方法である。
According to a seventh aspect of the present invention, polymer fine particles produced by reversed-phase suspension polymerization are particles having an average particle size of 100 μm or less in a saturated swelling state with water and a particle size of 150 μm or more in a saturated swelling state with water. The method for producing polymer fine particles according to any one of the first to sixth inventions, wherein the proportion is 1.0% by mass or less of polymer fine particles.
In the eighth invention, the polymer fine particles produced by reverse phase suspension polymerization have a water absorption ratio of 5 to 50 times, an average particle diameter in a saturated swelling state with water is 5 to 70 μm, and with water The method for producing polymer fine particles according to any one of the first to sixth inventions, wherein the proportion of particles having a particle diameter of 150 μm or more in a saturated swollen state is 0.3% by mass or less.
本発明の製造方法によれば、従来の方法と比較して格段に重合体微粒子の粒径が揃った、高品質の球状の親水性の重合体微粒子を、極めて高い分散安定性、重合安定性を維持しながら、重合時や重合後に重合体粒子の凝集、塊化、重合装置への付着などを生ずることなく生産性良く製造することができる。そして、本発明の製造方法では、多官能ビニル系単量体を多量に用いて架橋度の高い親水性架橋重合体微粒子を製造する場合であっても、重合体粒子の凝集、塊化、重合装置への付着などを生ずることなく、粒径の揃った高品質の親水性架橋重合体微粒子を生産性よく製造することができる。さらに、生産性を高めるために、製造をスケールアップした条件で実施した場合にも、本発明の製造方法は品質の高い重合体微粒子を製造することができる。 According to the production method of the present invention, high-quality spherical hydrophilic polymer fine particles having extremely uniform particle diameters of polymer fine particles compared with conventional methods are obtained with extremely high dispersion stability and polymerization stability. Thus, the polymer particles can be produced with high productivity without causing aggregation or agglomeration of the polymer particles or adhesion to the polymerization apparatus during or after the polymerization. And, in the production method of the present invention, even when hydrophilic crosslinked polymer fine particles having a high degree of crosslinking are produced using a large amount of polyfunctional vinyl monomer, the polymer particles are aggregated, agglomerated and polymerized. High-quality hydrophilic crosslinked polymer fine particles having a uniform particle size can be produced with high productivity without causing adhesion to the apparatus. Furthermore, even when the production is carried out under scaled up conditions in order to increase productivity, the production method of the present invention can produce high-quality polymer particles.
以下、本発明の実施形態について詳細に説明する。
本発明における「ビニル系単量体の逆相懸濁重合」は、油相を分散媒とし水相を分散質とする逆相懸濁重合を意味する。一般的には、親水性ビニル系単量体を用いて逆相懸濁重合する場合は、油相（疎水性有機溶媒よりなる分散媒）中に水相（親水性ビニル系単量体の水溶液）が水滴状に懸濁したＷ／Ｏ型の逆相懸濁重合で重合体微粒子を製造する。
本発明のビニル系単量体の逆相懸濁重合は、分散安定剤の存在下、油溶性酸化剤と水溶性還元剤を使用してビニル系単量体の逆相懸濁重合を行うものである。
Hereinafter, embodiments of the present invention will be described in detail.
The “reverse phase suspension polymerization of vinyl monomer” in the present invention means reverse phase suspension polymerization in which an oil phase is a dispersion medium and an aqueous phase is a dispersoid. Generally, when reverse phase suspension polymerization is performed using a hydrophilic vinyl monomer, an aqueous phase (an aqueous solution of a hydrophilic vinyl monomer) is contained in an oil phase (a dispersion medium composed of a hydrophobic organic solvent). Polymer fine particles are produced by W / O-type reverse phase suspension polymerization in which water is suspended in the form of water droplets.
The reverse phase suspension polymerization of the vinyl monomer of the present invention is a reverse phase suspension polymerization of a vinyl monomer using an oil-soluble oxidizing agent and a water-soluble reducing agent in the presence of a dispersion stabilizer. It is.
本発明の製造方法として好ましい方法は、分散安定剤と疎水性有機溶媒により調製調整した油相を仕込んだ反応液に、予めビニル系単量体（およびその中和物）と水を攪拌して均一に溶解させて調製した単量体混合物を仕込み、水溶性還元剤を供給した後に油溶性酸化剤を供給することで重合を開始させることである。 A preferable method for the production method of the present invention is to stir a vinyl monomer (and its neutralized product) and water in advance in a reaction solution charged with an oil phase prepared and adjusted with a dispersion stabilizer and a hydrophobic organic solvent. The polymerization is started by charging a monomer mixture prepared by uniformly dissolving, supplying a water-soluble reducing agent, and then supplying an oil-soluble oxidizing agent.
本発明の逆相懸濁重合に用いるビニル系単量体としては、ラジカル重合性の親水性ビニル系単量体であればいずれでもよく、特に制限されない。例えば、カルボキシル基、アミノ基、リン酸基、スルホン酸基、アミド基、水酸基、４級アンモニウム基などの親水性基を有する親水性ビニル系単量体を使用することができる。これらの中でもカルボキシル基、スルホン酸基およびアミド基を有する親水性ビニル系単量体が、親水性が高く、吸水性能、保水性能に優れた重合体微粒子が得られるために好ましい。 The vinyl monomer used in the reverse phase suspension polymerization of the present invention is not particularly limited as long as it is a radical polymerizable hydrophilic vinyl monomer. For example, a hydrophilic vinyl monomer having a hydrophilic group such as a carboxyl group, an amino group, a phosphoric acid group, a sulfonic acid group, an amide group, a hydroxyl group, or a quaternary ammonium group can be used. Among these, a hydrophilic vinyl monomer having a carboxyl group, a sulfonic acid group, and an amide group is preferable because polymer fine particles having high hydrophilicity and excellent water absorption performance and water retention performance can be obtained.
親水性ビニル系単量体の具体例としては、（メタ）アクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、イタコン酸モノブチル、マレイン酸モノブチル、シクロヘキサンジカルボン酸などのカルボキシル基を有するビニル系単量体またはそれらの（部分）アルカリ中和物；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミドなどのアミノ基を有するビニル系単量体またはそれらの（部分）酸中和物、もしくは（部分）４級化物；Ｎ−ビニルピロリドン、アクリロイルモルホリン；アシッドホスホオキシエチルメタクリレート、アシッドホスホオキシプロピルメタクリレート、３−クロロ−２−アシッドホスホオキシプロピルメタクリレートなどのリン酸基を有するビニル系単量体またはそれらの（部分）アルカリ中和物；２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸、２−スルホエチル（メタ）アクリレート、２−（メタ）アクリロイルエタンスルホン酸、アリルスルホン酸、スチレンスルホン酸、ビニルスルホン酸、アリルホスホン酸、ビニルホスホン酸などのスルホン酸基またはホスホン酸基を有するビニル系単量体またはそれらの（部分）アルカリ中和物；（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−アルコキシメチル（メタ）アクリルアミド、（メタ）アクリロニトリル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピルなどのノニオン性親水性単量体を挙げることができ、これらの１種または２種以上を用いることができる。 Specific examples of hydrophilic vinyl monomers include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconic acid, monobutyl maleate, cyclohexanedicarboxylic acid, and other vinyl monomers having a carboxyl group. Monomers or their (partial) alkali neutralized products; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylamide and other vinyl monomers having amino groups, or (partial) acid neutralized products or (partial) quaternized products; N-vinylpyrrolidone, acryloylmorpholine; Oxyethyl methacrylate, acid phosphooxypropi Methacrylate, vinyl monomers having a phosphate group such as 3-chloro-2-acid phosphooxypropyl methacrylate, or their (partially) alkali neutralized products; 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, 2- (meth) acryloylethanesulfonic acid, allyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, allyl phosphonic acid, vinyl phosphonic acid and other vinyl-based phosphonic acid groups Monomers or their (partially) alkali neutralized products; (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N-methylol (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, (meta ) Acrylonitrile Can be used (meth) acrylate, hydroxypropyl can be mentioned nonionic hydrophilic monomers such as (meth) acrylic acid hydroxypropyl, one or more of these.
これらの中でも、（メタ）アクリル酸、（メタ）アクリルアミドおよび２−アクリルアミド−２−メチルプロパンスルホン酸の１種または２種以上を用いて逆相懸濁重合を行うことが、重合性に優れる点、および得られた重合体微粒子が吸水特性に優れる点から好ましく、特に好ましくは（メタ）アクリル酸である。 Among these, it is excellent in polymerizability to perform reverse phase suspension polymerization using one or more of (meth) acrylic acid, (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid. And the obtained polymer fine particles are preferable from the viewpoint of excellent water absorption properties, and (meth) acrylic acid is particularly preferable.
また、本発明では、逆相懸濁重合を行なうに当たって、ビニル系単量体として、上記した単官能の親水性ビニル系単量体のうちの１種または２種以上と共に、ラジカル重合性の不飽和基を２個以上有する多官能ビニル系単量体を使用することができる。
したがって、本発明でいう「ビニル系単量体」は、単官能ビニル系単量体および多官能ビニル系単量体の総称である。
In the present invention, in carrying out the reverse phase suspension polymerization, as the vinyl monomer, one or more of the above-mentioned monofunctional hydrophilic vinyl monomers are used together with the radical polymerizable non-polymerization property. A polyfunctional vinyl monomer having two or more saturated groups can be used.
Therefore, the “vinyl monomer” referred to in the present invention is a general term for monofunctional vinyl monomers and polyfunctional vinyl monomers.
多官能ビニル系単量体としては、上記親水性ビニル系単量体とラジカル重合可能な基を２個以上有するビニル系単量体であればいずれでもよく、具体例として、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド変性物のトリ（メタ）アクリレートなどのポリオール類のジまたはトリ（メタ）アクリレート、メチレンビス（メタ）アクリルアミドなどのビスアミド類、ジビニルベンゼン、アリル（メタ）アクリレートなどを挙げることができ、これらの１種または２種以上を用いることができる。 The polyfunctional vinyl monomer may be any vinyl monomer having at least two radically polymerizable groups with the hydrophilic vinyl monomer. Specific examples thereof include polyethylene glycol di (meta ) Acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate and other di- or tri- (meta) ) Bisamides such as acrylate and methylene bis (meth) acrylamide, divinylbenzene, allyl (meth) acrylate, and the like, and one or more of these may be used.
これらの中でも、多官能ビニル系単量体としてはポリエチレングリコールジアクリレートおよびメチレンビスアクリルアミドが、ベースをなす親水性ビニル系単量体および水の混合液に対する溶解度に優れ、高架橋密度を得るために使用量を多くする際に有利であり好ましく用いられ、特に好ましくはポリエチレングリコールジ（メタ）アクリレートである。 Among these, as the polyfunctional vinyl monomer, polyethylene glycol diacrylate and methylene bisacrylamide are used to obtain a high crosslink density with excellent solubility in a mixture of the hydrophilic vinyl monomer as a base and water. It is advantageous and preferably used when increasing the amount, and polyethylene glycol di (meth) acrylate is particularly preferred.
上記多官能ビニル系単量体の使用割合は、使用するビニル系単量体の種類、得られる重合体微粒子の用途などに応じて異なり得るが、重合体微粒子に架橋特性が必要な場合には、使用される単官能ビニル系単量体の合計１００モルに対して０．１〜１００モルであることが好ましく、０．２〜５０モルであることがより好ましく、０．５〜１０モルであることが更に好ましい。 The ratio of the polyfunctional vinyl monomer used may vary depending on the type of vinyl monomer used, the intended use of the resulting polymer fine particles, etc. , Preferably 100 to 100 mol, more preferably 0.2 to 50 mol, more preferably 0.5 to 10 mol with respect to 100 mol of the monofunctional vinyl monomers used. More preferably it is.
本発明の逆相懸濁重合における油相（分散媒）をなす疎水性有機溶媒として、例えば、炭素数６以上の脂肪族炭化水素溶媒、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素溶媒、オクタメチルシクロテトラシロキサンなどのシリコーン系溶媒などを用いることができ、特にヘキサン、シクロヘキサン、およびｎ−ヘプタンが、ビニル系単量体および水の溶解度が小さく、かつ重合後に除去することが容易であることから好ましく用いられる。 Examples of the hydrophobic organic solvent that forms the oil phase (dispersion medium) in the reversed-phase suspension polymerization of the present invention include, for example, aliphatic hydrocarbon solvents having 6 or more carbon atoms, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene. In addition, silicone solvents such as octamethylcyclotetrasiloxane can be used. In particular, hexane, cyclohexane, and n-heptane have low solubility in vinyl monomers and water, and can be easily removed after polymerization. It is preferably used because of its existence.
本発明の逆相懸濁重合では、親水性ビニル系単量体（およびその中和塩）は水に溶解させて水溶液にして重合系に加えるとよい。親水性ビニル系単量体を溶解した水溶液中における親水性ビニル系単量体の濃度は、５〜８０質量％、特に２０〜６０質量％であることが、逆相懸濁重合が円滑に行われ、かつ生産性も良好であることから好ましい。
逆相懸濁重合に用いる親水性ビニル系単量体が、カルボキシル基やスルホン酸基などの酸性基を有するビニル系単量体である場合は、親水性ビニル系単量体を水に加えた後、アンモニア水、水酸化ナトリウム水溶液、水酸化カリウム水溶液などのアルカリ水溶液でビニル系単量体中の酸性基を中和すると、親水性ビニル系単量体を良好に溶解した水溶液を調製することができる。
In the reverse-phase suspension polymerization of the present invention, the hydrophilic vinyl monomer (and its neutralized salt) is preferably dissolved in water to form an aqueous solution and added to the polymerization system. The concentration of the hydrophilic vinyl monomer in the aqueous solution in which the hydrophilic vinyl monomer is dissolved is 5 to 80% by mass, particularly 20 to 60% by mass. And good productivity.
When the hydrophilic vinyl monomer used for the reverse phase suspension polymerization is a vinyl monomer having an acidic group such as a carboxyl group or a sulfonic acid group, the hydrophilic vinyl monomer was added to water. Then, neutralize the acidic group in the vinyl monomer with an aqueous alkaline solution such as aqueous ammonia, aqueous sodium hydroxide, or aqueous potassium hydroxide to prepare an aqueous solution that dissolves the hydrophilic vinyl monomer well. Can do.
本発明の製造方法において、分散安定剤は必須成分である。
分散安定剤の具体例としては、マクロモノマー型分散安定剤、ソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、ソルビトール脂肪酸エステル、ポリオキシエチレンアルキルエーテル等のノニオン性界面活性剤が挙げられる。
これらの中でも、マクロモノマー型分散安定剤を用いることが好ましい。マクロモノマー型分散安定剤は、ビニル系単量体由来の重合体の末端にラジカル重合性不飽和基を有するものである。
In the production method of the present invention, the dispersion stabilizer is an essential component.
Specific examples of the dispersion stabilizer include macromonomer type dispersion stabilizers, sorbitan fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, sorbitol fatty acid esters, polyoxyethylene alkyl ethers and other nonionic surfactants.
Among these, it is preferable to use a macromonomer type dispersion stabilizer. The macromonomer type dispersion stabilizer has a radically polymerizable unsaturated group at the end of a polymer derived from a vinyl monomer.
また、マクロモノマー型分散安定剤とソルビタンモノオレエートおよびソルビタンモノパルミテートなどの、ＨＬＢが３〜８である比較的疎水性が高いノニオン性界面活性剤を併用することが好ましく、これらは、１種を併用しても、２種以上を併用しても良い。 Further, it is preferable to use a macromonomer type dispersion stabilizer in combination with a relatively hydrophobic nonionic surfactant having an HLB of 3 to 8, such as sorbitan monooleate and sorbitan monopalmitate. Two or more species may be used in combination.
前記マクロモノマー型分散安定剤として好ましいマクロモノマーは、ビニル系単量体を１５０〜３５０℃でラジカル重合して得られる、ビニル系単量体由来の重合体の末端に式（１）；Ｈ２Ｃ＝Ｃ（Ｘ）−（式中、Ｘは１価の極性基）で表されるα置換型ビニル基を有するマクロモノマーおよび／またはビニル系単量体由来の重合体の末端に（メタ）アクリロイル基を有するマクロモノマーが、分散安定剤としての機能に優れていて好適であり、マクロモノマーの重量平均分子量は１０００〜３００００であることが好ましく、マクロモノマーは親水性ビニル系単量体由来の構造単位と疎水性ビニル系単量体由来の構造単位の両方を有していることが好ましく、その際の疎水性ビニル系単量体由来の構造単位としては、（メタ）アクリル酸の炭素数８以上のアルキルエステルに由来する構造単位が好ましく、親水性ビニル系単量体由来の構造単位としてはカルボキシル基を有するビニル系単量体に由来する構造単位が好ましい。 A preferred macromonomer as the macromonomer type dispersion stabilizer is represented by formula (1); H 2 at the end of a polymer derived from a vinyl monomer obtained by radical polymerization of a vinyl monomer at 150 to 350 ° C. At the end of a polymer derived from a macromonomer and / or vinyl monomer having an α-substituted vinyl group represented by C = C (X)-(where X is a monovalent polar group) A macromonomer having an acryloyl group is suitable because of its excellent function as a dispersion stabilizer, and the weight average molecular weight of the macromonomer is preferably 1000 to 30000. The macromonomer is derived from a hydrophilic vinyl monomer. It is preferable to have both a structural unit and a structural unit derived from a hydrophobic vinyl monomer, and the structural unit derived from the hydrophobic vinyl monomer at that time is (meth) acrylic acid. A structural unit derived from an alkyl ester having 8 or more carbon atoms is preferred, and a structural unit derived from a vinyl monomer having a carboxyl group is preferred as the structural unit derived from a hydrophilic vinyl monomer.
特に、マクロモノマー型分散安定剤を使用して、親水性ビニル系単量体を逆相懸濁重合させて親水性の重合体微粒子を製造する際には、単官能化合物と共に多官能ビニル系単量体を用いることが好ましく、それによって強度や形状保持性の向上した親水性の架橋した重合体微粒子が得られる。 In particular, when a hydrophilic polymer fine particle is produced by reverse-phase suspension polymerization of a hydrophilic vinyl monomer using a macromonomer type dispersion stabilizer, a polyfunctional vinyl monomer is used together with a monofunctional compound. It is preferable to use a monomer, whereby hydrophilic cross-linked polymer fine particles having improved strength and shape retention are obtained.
分散安定剤は分散媒（油相）である疎水性有機溶媒中に溶解、もしくは均一分散させて重合系に加えることが好ましい。
分散安定剤の使用量は、良好な分散安定性を維持しながら、粒径の揃った親水性重合体微粒子を得るために、ビニル系単量体の合計１００質量部に対して、０．１〜５０質量部であることが好ましく、０．２〜２０質量部であることがより好ましく、０．５〜１０質量部であることが更に好ましい。分散安定剤の使用量が少なすぎると、重合系でのビニル系単量体および生成した重合体微粒子の分散安定性が不良になり、生成した重合体微粒子同士の凝集、沈降、粒径のばらつきが生じ易くなる。一方、分散安定剤の使用量が多すぎると、副生微粒子（１μｍ以下）の生成量が多くなる場合がある。
The dispersion stabilizer is preferably added to the polymerization system after being dissolved or uniformly dispersed in a hydrophobic organic solvent which is a dispersion medium (oil phase).
In order to obtain hydrophilic polymer fine particles having a uniform particle size while maintaining good dispersion stability, the amount of the dispersion stabilizer used is 0.1 with respect to a total of 100 parts by mass of the vinyl monomer. It is preferable that it is -50 mass parts, It is more preferable that it is 0.2-20 mass parts, It is still more preferable that it is 0.5-10 mass parts. If the amount of the dispersion stabilizer used is too small, the dispersion stability of the vinyl monomer in the polymerization system and the generated polymer particles will be poor, and the generated polymer particles will aggregate, settle, and the particle size will vary. Is likely to occur. On the other hand, if the amount of the dispersion stabilizer used is too large, the amount of by-product fine particles (1 μm or less) produced may increase.
本発明の逆相懸濁重合では、重合系における油相（分散媒）：水相（分散質）の質量比が９９：１〜２０：８０、特に９５：５〜３０：７０になるようにして重合を行うことが、生産性と重合時の分散安定性、および重合体微粒子の粒子径制御が両立できる点から好ましい。 In the reverse phase suspension polymerization of the present invention, the mass ratio of the oil phase (dispersion medium) to the water phase (dispersoid) in the polymerization system is 99: 1 to 20:80, particularly 95: 5 to 30:70. It is preferable to carry out the polymerization from the viewpoint of achieving both productivity, dispersion stability during polymerization, and control of the particle size of the polymer fine particles.
本発明の逆相懸濁重合は撹拌下に行なうことが好ましく、攪拌翼やバッフルを設置した反応槽で反応を行なうことが好ましい。攪拌翼としては、アンカー翼およびパドル翼が好ましく、特にパドル翼が好ましい。一般的に懸濁重合は攪拌動力に左右され、攪拌動力が低いと目標とする粒子径の重合体微粒子が得られないか、あるいはモノマー水溶液滴同士の合一を抑えることができず、きれいな球状微粒子が得られない、あるいは凝集粒子が多数発生するなどの問題が起こることがある。
本発明における反応槽における単位体積当たりの攪拌動力は０．５ｋｗ／ｍ３以上であることが好ましく、特に好ましくは、１．０ｋｗ／ｍ３以上である。
The reverse phase suspension polymerization of the present invention is preferably carried out with stirring, and the reaction is preferably carried out in a reaction vessel equipped with stirring blades and baffles. As the stirring blade, an anchor blade and a paddle blade are preferable, and a paddle blade is particularly preferable. In general, suspension polymerization depends on the stirring power, and if the stirring power is low, polymer fine particles having a target particle size cannot be obtained, or coalescence of monomer aqueous solution droplets cannot be suppressed, and a clean spherical shape is obtained. There may be a problem that fine particles cannot be obtained or a large number of aggregated particles are generated.
Preferably the stirring power per unit volume in the reaction vessel in the present invention is 0.5 kw / m 3 or more, and particularly preferably 1.0 kw / m 3 or more.
本発明の逆相懸濁重合では、重合開始剤として油溶性酸化剤と水溶性還元剤を使用するレドックス系開始剤を使用する。レドックス反応は低温での重合開始が可能であり、重合反応液中のビニル系単量体濃度を高くすること、また重合速度を大きくすることが可能となるため、生産性、および生成重合体の分子量を高くすることが可能となる。 In the reverse phase suspension polymerization of the present invention, a redox initiator that uses an oil-soluble oxidizing agent and a water-soluble reducing agent is used as a polymerization initiator. The redox reaction can start polymerization at a low temperature, and the vinyl monomer concentration in the polymerization reaction solution can be increased and the polymerization rate can be increased. It becomes possible to increase the molecular weight.
上記のとおり、逆相懸濁重合では分散安定剤を溶解または分散させた疎水性有機溶媒が連続相（油相）として用いられるので、油溶性酸化剤とは、これらの連続相に溶解する酸化剤を意味する。 As described above, in reverse phase suspension polymerization, a hydrophobic organic solvent in which a dispersion stabilizer is dissolved or dispersed is used as a continuous phase (oil phase). Therefore, an oil-soluble oxidant is an oxidation that dissolves in these continuous phases. Means an agent.
本発明における油溶性酸化剤としては、日本工業規格Ｚ７２６０−１０７やＯＥＣＤ ＴＥＳＴ Ｇｕｉｄｅｌｉｎｅ１０７に定められるオクタノール／水分配係数（ｌｏｇＰｏｗ）が−１．４以上のものが好ましく、０．０以上のものがさらに好ましく、１．０以上のものが特に好ましい。 As the oil-soluble oxidant in the present invention, those having an octanol / water partition coefficient (logPow) of -1.4 or more as defined in Japanese Industrial Standard Z7260-107 and OECD TEST Guideline 107 are preferred, and those having 0.0 or more are further preferred. Preferably, 1.0 or more is particularly preferable.
具体例としてｔ−ブチルヒドロパーオキサイド（ｌｏｇＰｏｗ＝１．３）、ジ−ｔ−ブチルヒドロパーオキサイド、ｔ−ヘキシルヒドロパーオキサイド、ジ−ｔ−アミルパーオキサイド、クメンヒドロパーオキサイド（ｌｏｇＰｏｗ＝２．２）、ジクミルパーオキサイド（ｌｏｇＰｏｗ＝５．５）、ｔ−ブチルクミルパーオキサイド、ｔ−ブチルパーオキシピバレート、過酸化ベンゾイル（ｌｏｇＰｏｗ＝３．５）、過酸化ラウロイルなどの有機過酸化物が挙げられる。これらの中でもｔ−ブチルヒドロパーオキサイドおよびクメンヒドロパーオキサイドが好ましく、特に好ましくはクメンヒドロパーオキサイドである。 Specific examples include t-butyl hydroperoxide (log Pow = 1.3), di-t-butyl hydroperoxide, t-hexyl hydroperoxide, di-t-amyl peroxide, cumene hydroperoxide (log Pow = 2. 2) Organic peroxides such as dicumyl peroxide (logPow = 5.5), t-butylcumyl peroxide, t-butylperoxypivalate, benzoyl peroxide (logPow = 3.5), lauroyl peroxide Is mentioned. Among these, t-butyl hydroperoxide and cumene hydroperoxide are preferable, and cumene hydroperoxide is particularly preferable.
水溶性還元剤としては、レドックス重合開始剤に使用する還元剤として既知の還元剤が使用できるが、これらの中でも、亜硫酸ナトリウム、亜硫酸水素ナトリウム、ハイドロサルファイトナトリウムが好ましく、特に好ましくはハイドロサルファイトナトリウムである。なお、これらの水溶性還元剤は空気と接触することによって徐々に失活するため、所望の重合開始タイミングの数分前に水に溶解し、添加することが好ましい。 As the water-soluble reducing agent, known reducing agents can be used as the reducing agent used in the redox polymerization initiator. Among these, sodium sulfite, sodium bisulfite, and sodium hydrosulfite are preferable, and hydrosulfite is particularly preferable. Sodium. In addition, since these water-soluble reducing agents are gradually deactivated by contact with air, it is preferable to dissolve and add to water several minutes before the desired polymerization start timing.
油溶性酸化剤と水溶性還元剤は、必ず先に水溶性還元剤を反応器に供給した後に、油溶性酸化剤を反応器に供給する必要がある。水溶性還元剤を水溶化して反応器に供給した後、０．５〜１５分以内に油溶性酸化剤を供給して重合させるのが好ましく、１〜５分以内に油溶性酸化剤を供給することがより好ましい。 The oil-soluble oxidizing agent and the water-soluble reducing agent must be supplied to the reactor after the water-soluble reducing agent is first supplied to the reactor. After water-soluble reducing agent is made water-soluble and supplied to the reactor, it is preferable to polymerize by supplying an oil-soluble oxidant within 0.5 to 15 minutes, and supply an oil-soluble oxidant within 1 to 5 minutes. It is more preferable.
また、油溶性酸化剤の全量を２０秒〜１２０秒の時間をかけて反応器に供給することが好ましく、特に好ましくは２０秒〜６０秒である。
油溶性酸化剤の供給時間が２０秒よりも供給時間が短い場合、酸化剤の供給に対して拡散が追いつかず、ラジカルの発生が局部的に起こって凝集物が発生するなどの不具合が起こりやすくなる場合があり、好ましくない。また１２０秒よりも長い場合、還元剤が別の機構で分解消費されることによって、一部の酸化剤が未反応のまま系内に残ってしまう場合がある。酸化剤が未反応のまま残存すると、後の共沸脱水工程や乾燥工程などで凝集物を発生させるなど、不具合の原因となる場合があるため好ましくない。
水溶性還元剤の供給時間に関しては特に制限は無いが、一般に還元剤は空気などとの接触により分解しやすいため、１５分間以内で供給するのが好ましい。
The total amount of the oil-soluble oxidant is preferably supplied to the reactor over a period of 20 seconds to 120 seconds, particularly preferably 20 seconds to 60 seconds.
When the supply time of the oil-soluble oxidant is shorter than 20 seconds, the diffusion does not catch up with the supply of the oxidant, and the generation of radicals occurs locally and the occurrence of agglomerates is likely to occur. This is not preferable. If it is longer than 120 seconds, the reducing agent is decomposed and consumed by another mechanism, so that a part of the oxidizing agent may remain unreacted in the system. If the oxidizing agent remains unreacted, it is not preferable because it may cause problems such as generation of aggregates in a subsequent azeotropic dehydration step or drying step.
The supply time of the water-soluble reducing agent is not particularly limited, but in general, since the reducing agent is easily decomposed by contact with air or the like, it is preferably supplied within 15 minutes.
また、油溶性酸化剤は反応液の液面より下部に位置する供給口から反応器に供給することが好ましい。一般に重合触媒の投入口は反応器の上部に取り付けられており、この投入口から反応液の液面に重合触媒を一括または連続的に供給するが、本発明においては、重合触媒を反応器側面に接続された配管を通して反応液中に供給する方法が、触媒の均一拡散の観点から好ましい。
供給口の位置は、常時反応液中に浸かる位置にあれば制限は無いが、攪拌翼上端または
下端から垂直方向の高さにして±１ｍ以内の位置にあるのが好ましく、±５０ｃｍ以内の位置にあるのがより好ましい。
油溶性酸化剤を供給する方法としては、反応液の液面より下部に位置する供給口に通じる配管を通してポンプ、あるいは窒素のような不活性ガスのガス圧で供給する方法が挙げられる。
The oil-soluble oxidant is preferably supplied to the reactor from a supply port located below the liquid level of the reaction solution. In general, the polymerization catalyst inlet is attached to the upper part of the reactor, and the polymerization catalyst is supplied to the liquid level of the reaction liquid from this inlet in a batch or continuously. A method of supplying the reaction solution through a pipe connected to the catalyst is preferable from the viewpoint of uniform diffusion of the catalyst.
The position of the supply port is not limited as long as it is always immersed in the reaction solution, but it is preferably within ± 1 m from the top or bottom of the stirring blade in the vertical direction, and within ± 50 cm. More preferably.
Examples of the method for supplying the oil-soluble oxidant include a method for supplying the oil-soluble oxidant at a gas pressure of an inert gas such as a pump through a pipe leading to a supply port located below the reaction liquid level.
上記重合開始剤の使用量は、使用するビニル系単量体の種類、得られる重合体微粒子の粒径や分子量などに応じて調整することができるが、ビニル系単量体の合計量１００モルに対して、油溶性酸化剤の使用量は０．００１〜０．１５モルであることが好ましく、特に好ましくは０．００３〜０．０７モルである。
また、油溶性酸化剤と水溶性還元剤の比率は特に限定されないが、モル比率で油溶性酸化剤：水溶性還元剤が１．０：０．２５〜１５．０であることが好ましく、特に好ましくは１．０：１．０〜１０．０である。
上記範囲を外れると、単量体の反応率が低下したり、粒子を構成する重合体の鎖長が短くなったり、重量終了後も触媒が残存するなどによって、凝集物が発生するなどの不具合が生じる恐れがある。
The amount of the polymerization initiator used can be adjusted according to the type of vinyl monomer used, the particle size and molecular weight of the resulting polymer fine particles, etc., but the total amount of vinyl monomers is 100 mol. On the other hand, the amount of the oil-soluble oxidant is preferably 0.001 to 0.15 mol, particularly preferably 0.003 to 0.07 mol.
The ratio of the oil-soluble oxidizing agent and the water-soluble reducing agent is not particularly limited, but the oil-soluble oxidizing agent: water-soluble reducing agent is preferably 1.0: 0.25 to 15.0 in terms of molar ratio, Preferably it is 1.0: 1.0-10.0.
If it is out of the above range, the reaction rate of the monomer is reduced, the chain length of the polymer constituting the particles is shortened, or the catalyst remains even after the end of the weight, etc. May occur.
本発明の逆相懸濁重合は、重合を開始する際の反応液の温度は０〜４０℃とするのが好ましく、５〜３０℃とするのがより好ましく、１０〜２５℃とするのが特に好ましい。反応開始温度が０℃より低い場合は重合設備や反応溶液の凍結が問題となり、また冷却に必要なコストが多大なものとなる。一方、反応開始温度が４０℃を超える場合は、安全面から、供給する単量体の量を減少させる必要があり、生産コストが多大なものとなる。 In the reverse phase suspension polymerization of the present invention, the temperature of the reaction liquid at the start of polymerization is preferably 0 to 40 ° C, more preferably 5 to 30 ° C, and more preferably 10 to 25 ° C. Particularly preferred. When the reaction start temperature is lower than 0 ° C., freezing of the polymerization equipment and the reaction solution becomes a problem, and the cost required for cooling becomes great. On the other hand, when the reaction start temperature exceeds 40 ° C., it is necessary to reduce the amount of monomer to be supplied from the viewpoint of safety, resulting in a great production cost.
本発明の製造方法において、得られる重合体微粒子の平均粒子径は２〜１５０μｍであることが好ましく、２〜１００μｍであることがさらに好ましく、５〜７０μｍであることがより好ましい。平均粒子径が２μｍ未満であると滑り性やブロッキング防止機能が不十分な粒子になる恐れがあり、１５０μｍを超える場合は、大粒子により外観不良や手触り感の悪化、配合した材料の強度低下などの問題が発生する恐れがある。なお、重合体微粒子の大きさが小さくなるほど、連続相と分散相の界面面積が大きくなるため、分散安定剤の安定化効果がより必要となる。
また、重合体微粒子の大きさとしては、使用される条件下での大きさが重要となる。重合体微粒子が水膨潤粒子として応用される場合、水膨潤時の大きさが上記範囲にあることが好ましい。
In the production method of the present invention, the average particle size of the polymer fine particles obtained is preferably 2 to 150 μm, more preferably 2 to 100 μm, and even more preferably 5 to 70 μm. If the average particle size is less than 2 μm, there is a risk that the slipperiness or anti-blocking function may be insufficient, and if it exceeds 150 μm, large particles may deteriorate the appearance or feel, and decrease the strength of the blended material. May cause problems. In addition, since the interface area of a continuous phase and a dispersed phase becomes large, so that the magnitude | size of polymer fine particle becomes small, the stabilization effect of a dispersion stabilizer is needed more.
The size of the polymer fine particles is important under the conditions used. When the polymer fine particles are applied as water-swelling particles, the size at the time of water swelling is preferably in the above range.
重合体微粒子は架橋されていることが好ましく、前述したように多官能ビニル単量体を共重合することにより微粒子を構成する重合体を架橋構造とすることができる。
なお、官能基を有するビニル単量体を逆相懸濁重合した後、架橋剤を反応させて架橋度を調整することも可能である。例として、カルボキシル基を有する単量体の重合体微粒子をエチレングリコールジグリシジルエーテルにより架橋する方法が挙げられる。
その他、多価金属イオンを介したイオン結合性架橋、放射線の照射等の方法により架橋した共有結合性架橋など公知の方法で重合体を架橋することができる。
The polymer fine particles are preferably crosslinked, and the polymer constituting the fine particles can be made into a crosslinked structure by copolymerizing the polyfunctional vinyl monomer as described above.
It is also possible to adjust the degree of crosslinking by reacting a vinyl monomer having a functional group with reverse phase suspension polymerization and then reacting with a crosslinking agent. As an example, a method of crosslinking polymer fine particles of a monomer having a carboxyl group with ethylene glycol diglycidyl ether can be mentioned.
In addition, the polymer can be cross-linked by a known method such as ion-bonding cross-linking via polyvalent metal ions or covalent cross-linking cross-linked by a method such as radiation irradiation.
上記の架橋方法で得られる重合体微粒子が、０．５ｍｏｌ％以上の架橋密度を有する重合体微粒子である場合、先に記載したような各種用途においてその特性を発揮することが出来るため、０．５ｍｏｌ％以上の架橋密度を有する重合体微粒子であることが好ましい。 When the polymer fine particles obtained by the above crosslinking method are polymer fine particles having a crosslink density of 0.5 mol% or more, the characteristics can be exhibited in various applications as described above. Polymer fine particles having a crosslinking density of 5 mol% or more are preferred.
本発明の逆相懸濁重合により重合体微粒子の分散液を得た後、公知の方法により重合体微粒子の乾燥粉末を得ることができる。分散液をそのまま加熱、および減圧処理し揮発分を除去し乾燥粉末を得る方法、また、ろ過や遠心分離により固液分離、洗浄を行い、分散安定剤や未反応単量体等を除去した後、乾燥を行う方法も選択できる。洗浄工程を行うことは、乾燥後の微粒子の一次分散性が向上するため好ましい。
また、逆相懸濁重合の場合、分散相に水を含むため乾燥前にあらかじめ共沸等により水を除去することが好ましい。水をあらかじめ除去することにより乾燥時の粒子間融着を防止でき、乾燥後粒子の一次分散性が向上する。
After obtaining a dispersion of polymer fine particles by reverse phase suspension polymerization of the present invention, a dry powder of polymer fine particles can be obtained by a known method. A method in which the dispersion is heated and decompressed to remove volatile matter to obtain a dry powder, or after solid-liquid separation and washing by filtration or centrifugation to remove dispersion stabilizers, unreacted monomers, etc. The method of drying can also be selected. It is preferable to perform the washing step because the primary dispersibility of the fine particles after drying is improved.
In the case of reverse phase suspension polymerization, since water is contained in the dispersed phase, it is preferable to remove water by azeotropic distillation or the like before drying. By removing water in advance, inter-particle fusion during drying can be prevented, and the primary dispersibility of the particles after drying is improved.
本発明の製造方法において、水で飽和膨潤した状態における平均粒子径が２〜１００μｍであり、かつ水で飽和膨潤した状態において１５０μｍ以上の粒径を示す粒子の割合が１．０質量％以下である重合体微粒子が円滑に製造できる。このような重合体微粒子は各種用途においてその特性を著しく発揮することが出来る。
さらに、５〜５０倍の吸水倍率を有し、水で飽和膨潤した状態での平均粒子径が５〜７０μｍであり、かつ水で飽和膨潤した状態において１５０μｍ以上の粒径を示す粒子の割合が０．３質量％以下である重合体微粒子も製造することが可能であり、この重合体は各種用途において、極めて優れた特性を発現する重合体微粒子となる。
In the production method of the present invention, the average particle size in the state of saturated swelling with water is 2 to 100 μm, and the proportion of particles having a particle size of 150 μm or more in the state of saturated swelling with water is 1.0% by mass or less. Certain polymer fine particles can be produced smoothly. Such polymer fine particles can remarkably exhibit the characteristics in various applications.
Furthermore, the proportion of particles having a water absorption ratio of 5 to 50 times, an average particle size in a state of saturated swelling with water of 5 to 70 μm, and a particle size of 150 μm or more in a state of saturated swelling with water It is also possible to produce polymer fine particles of 0.3% by mass or less, and this polymer becomes polymer fine particles that exhibit extremely excellent characteristics in various applications.
なお、本明細書における重合体微粒子の吸水倍率、水による飽和膨潤状態での平均粒径、および水による飽和膨潤状態における１５０μｍ以上の粒径を有する粒子の割合は、以下の実施例の項に記載する方法で測定または求めた値をいう。 In addition, the water absorption ratio of the polymer fine particles in this specification, the average particle size in the saturated swelling state with water, and the ratio of particles having a particle size of 150 μm or more in the saturated swelling state with water are described in the Examples section below. The value measured or determined by the method described.
以下、実施例に基づいて本発明を具体的に説明する。以下の記載において「部」は質量部を意味し、「％」は質量％を意味する。 Hereinafter, the present invention will be specifically described based on examples. In the following description, “part” means part by mass, and “%” means mass%.
製造例１：マクロモノマー組成物ＵＭ−１、およびＵＭ−１ＨＰの製造
オイルジャケットを備えた容量１０００ｍｌの加圧式攪拌槽型反応器のオイルジャケットの温度を２４０℃に保った。
単量体としてラウリルメタクリレート（以下、ＬＭＡ）７５．０部、アクリル酸（以下、ＡＡ）２５．０部、重合溶媒としてメチルエチルケトン（以下、ＭＥＫ）１０．０部、重合開始剤としてジターシャリーブチルパーオキサイド（以下、ＤＴＢＰ）０．４５部の比率で調整された単量体混合液を原料タンクに仕込んだ。
原料タンクの単量体混合液を反応器に供給を開始し、反応器内の重量が５８０ｇ、平均滞留時間が１２分となるように、単量体混合液の供給と反応混合液の抜き出しを行った。反応器内温度は２３５℃、反応器内圧は１．１ＭＰａとなるように調整を行った。反応器より抜き出した反応混合液は、２０ｋＰａに減圧され、２５０℃に保たれた薄膜蒸発機に連続的に供給し、単量体や溶剤等が留去されたマクロモノマー組成物として排出された。留去した単量体や溶剤等はコンデンサーで冷却し、留出液として回収した。
単量体混合液の供給開始後、反応器内温が２３５℃に安定してから６０分後を回収開始点とし、これから４８分間反応を継続してマクロモノマー組成物ＵＭ−１を回収した。この間、単量体混合液は反応器に２．３４ｋｇ供給され、薄膜蒸発機より１．９２ｋｇのマクロモノマー組成物が回収された。また留出タンクには０．３９ｋｇの留出液が回収された。
Production Example 1: Production of Macromonomer Compositions UM-1 and UM-1HP The temperature of the oil jacket of a 1000 ml pressurized stirred tank reactor equipped with an oil jacket was kept at 240 ° C.
75.0 parts of lauryl methacrylate (hereinafter referred to as LMA) as a monomer, 25.0 parts of acrylic acid (hereinafter referred to as AA), 10.0 parts of methyl ethyl ketone (hereinafter referred to as MEK) as a polymerization solvent, and ditertiary butylpar as a polymerization initiator A monomer mixed liquid adjusted at a ratio of 0.45 parts of oxide (hereinafter referred to as DTBP) was charged into a raw material tank.
Start supplying the monomer mixture from the raw material tank to the reactor, and supply the monomer mixture and remove the reaction mixture so that the weight in the reactor is 580 g and the average residence time is 12 minutes. went. The reactor internal temperature was adjusted to 235 ° C., and the reactor internal pressure was adjusted to 1.1 MPa. The reaction mixture extracted from the reactor was decompressed to 20 kPa, continuously supplied to a thin film evaporator maintained at 250 ° C., and discharged as a macromonomer composition from which monomers and solvents were distilled off. . Distilled out monomers and solvents were cooled with a condenser and recovered as a distillate.
After the start of the monomer mixture supply, 60 minutes after the reactor internal temperature was stabilized at 235 ° C., the recovery start point was set, and the reaction was continued for 48 minutes to recover the macromonomer composition UM-1. During this time, 2.34 kg of the monomer mixture was supplied to the reactor, and 1.92 kg of the macromonomer composition was recovered from the thin film evaporator. In addition, 0.39 kg of distillate was recovered in the distillate tank.
留出液をガスクロマトグラフにて分析したところ、留出液１００部に対して、ＬＭＡ３１．１部、ＡＡ１６．４部、その他溶剤等が５２．５部であった。
単量体混合液の供給量および組成、マクロモノマー組成物の回収量、留出液の回収量および組成より、単量体の反応率は９０．２％、マクロモノマー組成物ＵＭ−１の構成単量体組成比は、ＬＭＡ：ＡＡ＝７６．０／２４．０（質量比）と計算された。
When the distillate was analyzed by gas chromatography, LMA 31.1 parts, AA 16.4 parts, other solvents, etc. were 52.5 parts with respect to 100 parts of distillate.
From the amount and composition of the monomer mixture, the recovered amount of the macromonomer composition, the recovered amount and composition of the distillate, the monomer reaction rate is 90.2%, and the composition of the macromonomer composition UM-1 The monomer composition ratio was calculated as LMA: AA = 76.0 / 24.0 (mass ratio).
また、溶離液にテトラヒドロフランを用いたゲルパーミションクロマトグラフ（以下、ＧＰＣ）により、マクロモノマー組成物ＵＭ−１の分子量を測定したところ、ポリスチレン換算での重量平均分子量（以下、Ｍｗ）および数平均分子量（以下、Ｍｎ）は、それぞれ、３８００、および１８００であった。またマクロモノマー組成物の１Ｈ−ＮＭＲ測定より、マクロモノマー組成物中の末端エチレン性不飽和結合の濃度を測定した。１Ｈ−ＮＭＲ測定による末端エチレン性不飽和結合の濃度、ＧＰＣによるＭｎ、および構成単量体組成比より、マクロモノマー組成物ＵＭ−１の末端エチレン性不飽和結合導入率（以下、Ｆ値）を計算した結果、９７％であった。
製造したマクロモノマー組成物ＵＭ−１を適当量のｎ−ヘプタンに加温溶解した後、固形分３０．０±０．５％となるようにｎ−ヘプタン加え、マクロモノマー組成物ＵＭ−１のｎ−ヘプタン溶液ＵＭ−１ＨＰを製造した。なお、固形分は１５０℃、１時間加熱後の加熱算分率により測定した。
なお、単量体、重合溶剤、および重合開始剤等の各原料については、市販の工業用製品を精製等の処理を行うことなく、そのまま使用した。
Further, when the molecular weight of the macromonomer composition UM-1 was measured by gel permeation chromatography (hereinafter referred to as GPC) using tetrahydrofuran as an eluent, the weight average molecular weight (hereinafter referred to as Mw) and number average molecular weight in terms of polystyrene were measured. (Hereinafter, Mn) was 3800 and 1800, respectively. Also from the 1 H-NMR measurement of the macromonomer composition to determine the concentration of terminal ethylenically unsaturated bond of the macromonomer composition. Terminal ethylenically unsaturated bond introduction rate (hereinafter referred to as F value) of macromonomer composition UM-1 based on the concentration of terminal ethylenically unsaturated bond by 1 H-NMR measurement, Mn by GPC, and constituent monomer composition ratio Was calculated to be 97%.
The prepared macromonomer composition UM-1 was dissolved by heating in an appropriate amount of n-heptane, and then n-heptane was added so that the solid content was 30.0 ± 0.5%. An n-heptane solution UM-1HP was prepared. In addition, solid content was measured by the heating fraction after heating at 150 degreeC for 1 hour.
In addition, about each raw material, such as a monomer, a polymerization solvent, and a polymerization initiator, the commercially available industrial product was used as it was, without performing processes, such as refinement | purification.
実施例１：重合体微粒子Ｔ−１の製造
重合反応には、ピッチドパドル型攪拌翼および２本垂直バッフルからなる撹拌機構を有し、さらに温度計、還流冷却器、窒素導入管を備えた、容量２５０ｌの反応器を用いた。なお窒素導入管は反応器の外でふたつに分岐しており、一方からは窒素を、もう一方からはポンプを用いて重合触媒を供給できるようになっている。また、窒素導入管は攪拌翼上端とほぼ同じ高さの反応器壁面に接続されている。また、反応液の総体積が２２０ｌとなるように仕込みを行った。詳細を下記に述べる。
Example 1: Production of polymer fine particles T-1 The polymerization reaction had a stirring mechanism comprising a pitched paddle type stirring blade and two vertical baffles, and further provided with a thermometer, a reflux condenser, and a nitrogen introduction tube. A 250 l reactor was used. The nitrogen introduction pipe is branched into two outside the reactor, and nitrogen can be supplied from one side and a polymerization catalyst can be supplied from the other side using a pump. Further, the nitrogen introduction tube is connected to the reactor wall surface which is almost the same height as the upper end of the stirring blade. Moreover, it prepared so that the total volume of a reaction liquid might be 220l. Details are described below.
反応器内に分散安定剤として、製造例１で製造したＵＭ−１ＨＰ ４．７部（ＵＭ−１の純分として１．４部）およびソルビタンモノオレエート（花王製レオドールＡＯ−１０）２．０部、更に重合溶媒としてｎ−ヘプタン４００．３部を仕込み、溶液の温度を４０℃に維持しながら攪拌混合して油相調整した。油相は、４０℃で３０分間攪拌した後２０℃まで冷却した。
一方、別の容器にてＡＡ１００．０部、アロニックスＭ−２４３（東亞合成製、ポリエチレングリコールジアクリレート、平均分子量４２５）１３．０部（単官能単量体に対して２．２ｍｏｌ％に相当）、およびイオン交換水９５．０部を仕込み、攪拌、均一溶解させた。さらに混合液の温度を４０℃以下に保つように冷却しながら、２５％アンモニア水７０．８部をゆっくり加えて中和し単量体混合液を得た。
As a dispersion stabilizer in the reactor, 4.7 parts of UM-1HP produced in Production Example 1 (1.4 parts as a pure part of UM-1) and sorbitan monooleate (Leodol AO-10 manufactured by Kao) 2. 0 parts and 400.3 parts of n-heptane as a polymerization solvent were added, and the oil phase was adjusted by stirring and mixing while maintaining the temperature of the solution at 40 ° C. The oil phase was stirred at 40 ° C. for 30 minutes and then cooled to 20 ° C.
On the other hand, in a separate container, AA 100.0 parts, Aronix M-243 (manufactured by Toagosei Co., Ltd., polyethylene glycol diacrylate, average molecular weight 425) 13.0 parts (corresponding to 2.2 mol% with respect to the monofunctional monomer) And 95.0 parts of ion-exchanged water were added and stirred and dissolved uniformly. Further, while cooling so that the temperature of the mixed solution was kept at 40 ° C. or lower, 70.8 parts of 25% aqueous ammonia was slowly added to neutralize to obtain a monomer mixed solution.
攪拌回転数を１３０ｒｐｍに設定した後、得られた単量体混合液を反応器内に仕込み、単量体混合液が油相に分散した分散液を調整した。この際攪拌動力を測定したところ、１．３６ｋＷ／ｍ３であった。反応器内温を２０℃に保持し、分散液に窒素を吹き込むことで反応器内の酸素を除去した。単量体混合物の仕込みから、１時間４０分経過した時点で、ハイドロサルファイトナトリウム（Ｎａ）０．０４５部とイオン交換水０．７２部の水溶液を反応器上部に据え付けられた添加口から添加した。その３分後、パークミルＨ８０（日本油脂製、クメンハイドロパーオキサイドの８０％溶液）０．０３９部をｎ−ヘプタン３．１部で希釈した溶液を、窒素導入管を通じてポンプで供給した。なお供給は３０秒間で行った。供給開始時点から直ちに反応器内温が上昇し、重合が開始したことが確認された。内温の上昇は約２分間でピークに達し、その温度は６６．０℃であった。その後、反応液を室温まで冷却し、重合体微粒子Ｔ−１の油中分散液を得た。 After setting the stirring rotation speed to 130 rpm, the obtained monomer mixture was charged into the reactor to prepare a dispersion in which the monomer mixture was dispersed in the oil phase. At this time, the stirring power was measured and found to be 1.36 kW / m 3. The reactor internal temperature was maintained at 20 ° C., and nitrogen was blown into the dispersion to remove oxygen in the reactor. When 1 hour and 40 minutes have passed since the preparation of the monomer mixture, an aqueous solution of 0.045 part of hydrosulfite sodium (Na) and 0.72 part of ion-exchanged water was added from the addition port installed at the top of the reactor. did. Three minutes later, Parkmill H80 (manufactured by NOF Corporation, 80% solution of cumene hydroperoxide) 0.039 parts diluted with 3.1 parts of n-heptane was supplied by a pump through a nitrogen introduction tube. The supply was performed for 30 seconds. It was confirmed that the temperature inside the reactor immediately rose from the start of the supply, and the polymerization started. The increase in internal temperature reached a peak in about 2 minutes, and the temperature was 66.0 ° C. Thereafter, the reaction solution was cooled to room temperature to obtain a dispersion of polymer fine particles T-1 in oil.
Ｔ−１の油中分散液を反応器から抜き出す際、分散液は目開き７５μｍのフィルターを用いて濾過を行った。濾過性は良好で、濾過完了後のフィルターには目立った付着物は見られなかった。また、抜き出し終了後に反応器内壁面への樹脂付着程度を確認したところ、重合時の液面付近にわずかに付着が認められる程度であり、重合体微粒子Ｔ−１が安定に製造できることが確認された。 When the T-1 dispersion in oil was withdrawn from the reactor, the dispersion was filtered using a filter having an opening of 75 μm. The filterability was good, and no noticeable deposits were found on the filter after completion of filtration. Further, when the degree of resin adhesion to the inner wall surface of the reactor was confirmed after completion of the extraction, it was confirmed that slight adhesion was observed near the liquid surface during polymerization, and it was confirmed that the polymer fine particles T-1 could be stably produced. It was.
Ｔ−１の油中分散液を一部サンプリングし、デジタルマイクロスコープ（ハイロックス製、ＫＨ−３０００）にて倍率４２０倍で観察したところ、１０〜２０μｍ付近を中心とした分布を有する球状微粒子群が確認された。写真を図１に示す。複数の粒子が合一した凝集粒子群は観察されなかった。
また、油中分散液を１１０℃、１時間乾燥させたサンプルについて吸水倍率（重合体微粒子の分析条件（２）、参照）を測定した結果、２０．４倍であった。乾燥サンプルを大過剰のイオン交換水に分散し飽和膨潤させた後、倍率４２０倍で観察したところ、３０〜４０μｍ付近を中心とした分布を有する球状微粒子群が確認された。写真を図２に示す。
A part of T-1 dispersion in oil was sampled and observed with a digital microscope (Hilox, KH-3000) at a magnification of 420 times. A group of spherical fine particles having a distribution centered around 10 to 20 μm. Was confirmed. A photograph is shown in FIG. Aggregated particle groups in which a plurality of particles were combined were not observed.
Further, the water absorption ratio (see polymer microparticle analysis condition (2)) was measured for a sample obtained by drying the dispersion in oil at 110 ° C. for 1 hour, and the result was 20.4 times. When the dried sample was dispersed in a large excess of ion-exchanged water and saturated and swollen, and observed at a magnification of 420 times, a group of spherical fine particles having a distribution centered around 30 to 40 μm was confirmed. A photograph is shown in FIG.
また、水飽和膨潤させた重合体微粒子Ｔ−１について、レーザー回折／散乱式粒度分布計を用いて粒度分布測定（重合体微粒子の分析条件（３）、参照）を行った。得られた粒度分布は単一ピークであり、水飽和膨潤粒子径は３８．９μｍであった。重合体微粒子Ｔ−１は吸水性能を有し、かつ吸水膨潤時にも球状を保ち、水中で一次分散することが確認された。更にＴ−１をオイルバスにて加熱し、粒子内に含まれる水とヘプタンとを共沸させることによって脱水率９５％まで脱水した後に脱溶剤し、粉末化させたサンプルについて湿式篩残渣量（重合体微粒子の分析条件（４）、参照）を測定した結果、０．００４％であった。重合体微粒子Ｔ−１は、共沸脱水後に水飽和膨潤させた状態においても１５０μｍを超えるような粗大粒子が含まれていないことが確認された。結果を表１に示す。 Moreover, about the polymer fine particle T-1 which carried out the water saturation swelling, the particle size distribution measurement (Refer to analysis conditions (3) of polymer fine particle) was performed using the laser diffraction / scattering type particle size distribution meter. The obtained particle size distribution was a single peak, and the water-saturated swelling particle size was 38.9 μm. It was confirmed that the polymer fine particles T-1 had a water absorption performance, kept a spherical shape even during water absorption swelling, and were primarily dispersed in water. Further, T-1 is heated in an oil bath, and water and heptane contained in the particles are azeotroped to dehydrate to a dehydration rate of 95%. As a result of measuring analysis conditions (4) of polymer fine particles, it was 0.004%. It was confirmed that the polymer fine particles T-1 did not contain coarse particles exceeding 150 μm even in the state of water saturation swelling after azeotropic dehydration. The results are shown in Table 1.
表１において、「壁面付着状態」は反応終了後の反応器内面壁面への樹脂の付着を目視で観察した結果であり、○：ほとんど付着なし、△：液面部分に付着あり、×：全体に著しい付着あり、を示す。
また、「重合スラリー濾過性」は反応分散液を目開き７５μｍのフィルターで濾過を行った際の濾過性を観察した結果であり、○：フィルターの閉塞なし、△：１〜２回閉塞した、×：７５μｍで濾過できない、を示す。
また、「共沸脱水後の湿式篩残渣外観」は脱水して粉末化させたサンプルの湿式篩残渣を観察した結果であり、凝集物とは粒子が凝集した凝集物が存在することを示す。
In Table 1, “wall surface adhesion state” is the result of visual observation of resin adhesion on the inner wall surface of the reactor after completion of the reaction. ○: Almost no adhesion, Δ: Adhesion on the liquid surface part, ×: Overall Shows marked adhesion.
Further, “polymerization slurry filterability” is the result of observing the filterability when the reaction dispersion was filtered with a filter having an opening of 75 μm, ○: no filter clogging, Δ: clogged once or twice, X: Indicates that filtration cannot be performed at 75 μm.
“Appearance of wet sieving residue after azeotropic dehydration” is the result of observing the wet sieving residue of the dehydrated and pulverized sample, and the agglomerate indicates the presence of agglomerated particles.
実施例２：重合体微粒子Ｔ−２の製造
油溶性酸化剤パークミルＨ８０の供給時間を１０秒とした以外は実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 2 Production of Polymer Fine Particle T-2 Production was carried out in the same manner as in Example 1 except that the supply time of the oil-soluble oxidizer Park Mill H80 was 10 seconds. The results are shown in Table 1.
実施例３：重合体微粒子Ｔ−３の製造
油溶性酸化剤パークミルＨ８０の供給時間を１２０秒とした以外は実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 3 Production of Polymer Fine Particle T-3 Production was carried out in the same manner as in Example 1 except that the supply time of the oil-soluble oxidizer Park Mill H80 was 120 seconds. The results are shown in Table 1.
実施例４：重合体微粒子Ｔ−４の製造
油溶性酸化剤パークミルＨ８０の供給時間を１８０秒とした以外は実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 4 Production of Polymer Fine Particle T-4 Production was carried out in the same manner as in Example 1 except that the supply time of oil-soluble oxidizer Park Mill H80 was 180 seconds. The results are shown in Table 1.
実施例５：重合体微粒子Ｔ−５の製造
単量体混合物の仕込みから１時間４０分経過した時点でハイドロサルファイトＮａの水溶液を反応器上部の添加口から添加し、その３分後にパークミルＨ８０のｎ−ヘプタン溶液を、反応器上部に取り付けられた別の投入口からポンプを用いて３０秒間で供給した以外は、実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 5: Production of polymer fine particle T-5 When 1 hour and 40 minutes had elapsed from the preparation of the monomer mixture, an aqueous solution of hydrosulfite Na was added from the addition port at the top of the reactor, and 3 minutes later, Parkmill H80 The n-heptane solution was prepared in the same manner as in Example 1 except that it was supplied from another inlet attached to the top of the reactor using a pump for 30 seconds. The results are shown in Table 1.
実施例６：重合体微粒子Ｔ−６の製造
ＵＭ−１ＨＰ ４．７部（純分１．４部）／ソルビタンモノオレエート２．０部を使用する代わりに、ソルビタンモノオレエート３．４部を使用し、更に重合溶媒としてｎ−ヘプタン４０３．６部を使用した以外は実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 6: Preparation of polymer particulate T-6 UM-1HP 4.7 parts (1.4 parts pure) /3.4 parts sorbitan monooleate instead of 2.0 parts sorbitan monooleate Was used in the same manner as in Example 1 except that 403.6 parts of n-heptane was used as a polymerization solvent. The results are shown in Table 1.
実施例７：重合体微粒子Ｔ−７の製造
油溶性酸化剤として、パークミルＨ８０の代わりにパーブチルＨ６９（ＰＢＨ）（日本油脂製、ｔ−ブチルヒドロパーオキサイドの６９％溶液）を使用した以外は実施例１と同様の操作で製造を行った。結果を表１に示す。
Example 7: Production of polymer fine particles T-7 As an oil-soluble oxidant, perbutyl H69 (PBH) (manufactured by NOF Corporation, 69% solution of t-butyl hydroperoxide) was used instead of Parkmill H80. Production was carried out in the same manner as in Example 1. The results are shown in Table 1.
比較例１：重合体微粒子Ｔ−８の製造
５００ｍｌビーカーにアクリル酸１００ｇ、アロニックスＭ−２４３（東亞合成製、ポリエチレングリコールジアクリレート、平均分子量４２５）１３．０ｇ（単官能単量体に対して２．２ｍｏｌ％に相当）、及びイオン交換水９５．０ｇを仕込み、攪拌、均一溶解させた。さらに混合液の温度を４０℃以下に保つように冷却しながら、２５％アンモニア水７０．８ｇをゆっくり加えて中和し単量体混合液を得た。更に、ここに過硫酸アンモニウム塩０．３３ｇとイオン交換水４．９ｇとの水溶液を加え、均一に混合した。
次に、２ｌビーカーにショ糖脂肪酸エステル（三菱食品化学製、Ｓ−５７０とＳ−７７０との等量混合物）５ｇ、及びシクロヘキサン４９０．２ｇとを加え、攪拌しながら加温してショ糖脂肪酸エステルを溶解させた後、この溶液をピッチドパドル型攪拌翼及び２本垂直バッフルからなる撹拌機構を有する、容量２ｌのフラスコに加えた。ここに前述の単量体水溶液を加え、６００ｒｐｍで１時間攪拌し、油中水型分散液を作成した（反応液Ａ）。
一方、ピッチドパドル型攪拌翼及び２本垂直バッフルからなる撹拌機構を有し、さらに温度計、還流冷却器、及び窒素導入管を備えた、容量２ｌの別の反応器を用意し、これにショ糖脂肪酸エステル（三菱食品化学製、Ｓ−５７０とＳ−７７０との等量混合物）５ｇ、及びシクロヘキサン４９０．２ｇとを加えた。攪拌しながら８０℃に加温してショ糖脂肪酸エステルを溶解させ、更に、内部を窒素置換しながら溶液温度を８０℃に維持した（反応液Ｂ）。
反応液Ａ、反応液Ｂ共に６００ｒｐｍで攪拌しながら、反応液Ａを反応液Ｂへ滴下し、重合を開始させた。反応液Ａの全量を１時間で滴下する予定であったが、滴下開始から２０分程経過した時点からバッフル、及び反応器内壁に樹脂の付着が確認されるようになり、以後、時間の経過と共に付着ゲルが大きくなっていく様子が観察された。
モノマー水溶液の滴下を完了した後、６０分間そのまま加熱攪拌を続けた。得られたＴ−６の油中分散液を反応器から抜き出す際、目開き７５μｍのフィルターを用いて濾過を試みたが、すぐに閉塞し、濾過することができなかった。Ｔ−６の油中分散液を取り出して観察したところ、大部分が巨大な凝集塊となっており、目標とするような微粒子は得られないことがわかった。
Comparative Example 1: Production of polymer fine particles T-8 A 500 ml beaker was charged with 100 g of acrylic acid, Aronix M-243 (manufactured by Toagosei Co., Ltd., polyethylene glycol diacrylate, average molecular weight 425) 13.0 g (2 for monofunctional monomer) Equivalent to 2 mol%) and 95.0 g of ion-exchanged water were added and stirred and dissolved uniformly. Further, while cooling so that the temperature of the mixed solution was kept at 40 ° C. or lower, 70.8 g of 25% aqueous ammonia was slowly added to neutralize it to obtain a monomer mixed solution. Further, an aqueous solution of 0.33 g of ammonium persulfate and 4.9 g of ion-exchanged water was added thereto and mixed uniformly.
Next, 5 g of sucrose fatty acid ester (Mitsubishi Foods Chemical Co., Ltd., S-570 and S-770 equivalent mixture) and 490.2 g of cyclohexane are added to a 2 l beaker and heated with stirring to sucrose fatty acid. After the ester was dissolved, this solution was added to a 2 liter flask having a stirring mechanism consisting of a pitched paddle type stirring blade and two vertical baffles. The above monomer aqueous solution was added thereto and stirred at 600 rpm for 1 hour to prepare a water-in-oil dispersion (reaction solution A).
On the other hand, another reactor with a capacity of 2 liters having a stirring mechanism composed of a pitched paddle type stirring blade and two vertical baffles, and further equipped with a thermometer, a reflux condenser, and a nitrogen introduction tube was prepared. Fatty acid ester (Mitsubishi Foods Chemical Co., Ltd., an equivalent mixture of S-570 and S-770) 5 g and cyclohexane 490.2 g were added. While stirring, the mixture was heated to 80 ° C. to dissolve the sucrose fatty acid ester, and the solution temperature was maintained at 80 ° C. while replacing the inside with nitrogen (reaction solution B).
While stirring both the reaction liquid A and the reaction liquid B at 600 rpm, the reaction liquid A was added dropwise to the reaction liquid B to initiate polymerization. The total amount of the reaction liquid A was scheduled to be dripped in 1 hour, but from about 20 minutes after the start of dripping, the adhesion of the resin to the baffle and the inner wall of the reactor was confirmed, and thereafter, the passage of time At the same time, it was observed that the attached gel was enlarged.
After completion of the dropwise addition of the aqueous monomer solution, heating and stirring were continued for 60 minutes. When the obtained dispersion of T-6 in oil was withdrawn from the reactor, filtration was attempted using a filter having a mesh opening of 75 μm, but it was immediately clogged and could not be filtered. When the T-6 dispersion in oil was taken out and observed, it was found that most of the dispersion was a huge agglomerate, and the target fine particles could not be obtained.
比較例２：重合体微粒子Ｔ−９の製造
単量体混合物の仕込みから１時間４０分経過した時点でパークミルＨ８０のｎ−ヘプタン溶液をホッパーから添加し、その３分後にハイドロサルファイトＮａの水溶液を窒素導入管を通じてポンプで３０秒間で供給した以外は実施例１と同様の操作で製造を行った。
ハイドロサルファイトＮａ水溶液の供給を開始した時点から直ちに反応器内温が上昇し、約２分間で反応液の温度が４０℃に達したが、その時点で反応液の液面に大きなゲル塊が目視確認された。結果を表１に示す。
Comparative Example 2: Production of polymer fine particle T-9 When 1 hour and 40 minutes had elapsed from the preparation of the monomer mixture, an n-heptane solution of Parkmill H80 was added from the hopper, and 3 minutes later, an aqueous solution of hydrosulfite Na Was produced in the same manner as in Example 1 except that was supplied through a nitrogen introduction tube with a pump for 30 seconds.
The temperature inside the reactor immediately increased from the time when the supply of the aqueous hydrosulfite Na solution was started, and the temperature of the reaction solution reached 40 ° C. in about 2 minutes. At that point, a large gel lump was formed on the surface of the reaction solution. It was confirmed visually. The results are shown in Table 1.
参考試験：スケールアップ適性の確認
実施例および比較例において、２５０ｌ反応器で試験を行った結果を示した（Ｔ−８のみ２ｌ反応器）。更に、実施例１〜７および比較例１〜２の条件で製造スケールを変えて試験を行った結果を次の表２に示す。表２における評価条件は、上記表１と同様である。
Reference test: Confirmation of scale-up suitability In the examples and comparative examples, the results of tests with a 250 l reactor were shown (T-8 only 2 l reactor). Furthermore, the result of having tested by changing a manufacturing scale on the conditions of Examples 1-7 and Comparative Examples 1-2 is shown in following Table 2. The evaluation conditions in Table 2 are the same as in Table 1 above.
上記実施例における、重合体微粒子の分析条件（１）〜（４）は以下に記載のとおりである。
（１）固形分
測定サンプル約１ｇを秤量（ａ）し、次いで、無風乾燥機１５０℃、６０分間乾燥後の残分を測定（ｂ）し、以下の式より算出した。測定には秤量ビンを使用した。その他の操作については、ＪＩＳ Ｋ ００６７−１９９２（化学製品の減量及び残分試験方法）に準拠した。
固形分（％）＝（ｂ／ａ）×１００
The analysis conditions (1) to (4) of the polymer fine particles in the above examples are as described below.
(1) About 1 g of a solid content measurement sample was weighed (a), then the residue after drying for 60 minutes at 150 ° C. in an airless dryer was measured (b), and calculated from the following formula. A weighing bottle was used for the measurement. Other operations were in accordance with JIS K 0067-1992 (chemical product weight loss and residue test method).
Solid content (%) = (b / a) × 100
（２）吸水倍率
吸水倍率は以下の方法によって測定した。測定装置を図３に示す。
測定装置は図３における＜１＞〜＜３＞から構成される。
＜１＞ 空気抜きするための枝管が付いたビュレット１、ピンチコック２、シリコンチューブ３およびポリテトラフルオロエチレンチューブ４から成る。
＜２＞ ロート５の上に底面に多数の穴が空いた支柱円筒８、さらにその上に装置用濾紙１０が設置されている。
＜３＞ 重合体微粒子の試料６は２枚の試料固定用濾紙７に挟まれ、試料固定用濾紙は粘着テープ９によって固定される。なお、使用する濾紙は全てＡＤＶＡＮＴＥＣ Ｎｏ．２ 内径５５ｍｍである。
＜１＞と＜２＞とはシリコンチューブ３によって繋がれる。
また、ロート５および支柱円筒８は、ビュレット１に対する高さが固定されており、ビュレット枝管の内部に設置されたポリテトラフルオロエチレンチューブ４の下端と支柱円筒８の底面とが同じ高さになる様に設定されている（図３中の点線）。
(2) Water absorption ratio The water absorption ratio was measured by the following method. A measuring apparatus is shown in FIG.
The measuring device is composed of <1> to <3> in FIG.
<1> Consists of a burette 1 with a branch pipe for venting air, a
<2> A support cylinder 8 having a large number of holes in the bottom surface on the funnel 5, and a
<3> The sample 6 of polymer fine particles is sandwiched between two sample fixing filter papers 7, and the sample fixing filter papers are fixed by an adhesive tape 9. All filter papers used are ADVANTEC No. 2 The inner diameter is 55 mm.
<1> and <2> are connected by the silicon tube 3.
Further, the funnel 5 and the column cylinder 8 are fixed to the burette 1 at a fixed height, and the lower end of the polytetrafluoroethylene tube 4 installed inside the buret branch pipe and the bottom surface of the column cylinder 8 have the same height. (Dotted line in FIG. 3).
測定方法について以下に説明する。
＜１＞にあるピンチコック２を外し、ビュレット１の上部からシリコンチューブ３を通してイオン交換水を入れ、ビュレット１から装置用濾紙１０までイオン交換水１２で満たされた状態とする。次いで、ピンチコック２を閉じ、ビュレット枝管にゴム栓で接続されたポリテトラフルオロエチレンチューブ４から空気を除去する。こうして、ビュレット１から装置用濾紙１０までイオン交換水１２が連続的に供給される状態とする。
次に、装置用濾紙１０からにじみ出た余分なイオン交換水１２を除去した後、ビュレット１の目盛りの読み（ａ）を記録する。
測定試料の乾燥粉末０．１〜０．２ｇを秤量し、＜３＞にある様に、試料固定用濾紙７の中央部に均一に置く。もう１枚の濾紙でサンプルを挟み、粘着テープ９で２枚の濾紙を留め、サンプルを固定する。サンプルが固定された濾紙を＜２＞に示される装置用濾紙１０上に載置する。
次に、装置用濾紙１０上に蓋１１を載置した時点から、３０分間経過した後のビュレット１の目盛りの読み（ｂ）を記録する。
測定試料の吸水量と２枚の試料固定用濾紙７の吸水量の合計（ｃ）は（ａ−ｂ）で求められる。同様の操作により、吸水性ポリマー試料を含まない、２枚の濾紙７のみの吸水量を測定する（ｄ）。
上記操作を行い、吸水倍率を以下の式より計算した。なお、計算に使用する固形分は、（１）の方法により測定した値を使用した。
The measurement method will be described below.
The
Next, after removing the excess ion-exchanged
Weigh 0.1 to 0.2 g of the dry powder of the measurement sample and place it uniformly on the center of the sample fixing filter paper 7 as shown in <3>. The sample is sandwiched with another filter paper, and the two filter papers are fastened with the adhesive tape 9 to fix the sample. The filter paper on which the sample is fixed is placed on the
Next, the reading (b) of the scale of the bullet 1 after 30 minutes from the time when the
The sum (c) of the amount of water absorption of the measurement sample and the amount of water absorption of the two sample fixing filter papers 7 is obtained by (ab). By the same operation, the water absorption amount of only two filter papers 7 not including the water absorbent polymer sample is measured (d).
The above operation was performed, and the water absorption ratio was calculated from the following formula. In addition, the value measured by the method of (1) was used for solid content used for calculation.
（３）水膨潤粒子径
測定サンプル０．０２ｇにイオン交換水２０ｍｌを加え、十分に振り混ぜて、サンプルを均一分散させた。また粒子を水飽和膨潤状態とするために、３０分以上分散させた分散液について、レーザー回折散乱式粒度分布計（日機装製、ＭＴ−３０００）を用いて、超音波1分照射後に粒度分布測定を行った。測定時の循環分散媒にはイオン交換水を使用し、分散体の屈折率は１．５３とした。測定により得られた体積基準での粒度分布よりメジアン径（μｍ）を計算し、水膨潤粒子径とした。
(3) Water-swelling particle diameter 20 ml of ion-exchanged water was added to 0.02 g of the measurement sample, and the mixture was sufficiently shaken to uniformly disperse the sample. In order to make the particles into a water-saturated swelling state, the particle size distribution is measured after 1 minute of ultrasonic irradiation using a laser diffraction / scattering particle size distribution meter (manufactured by Nikkiso, MT-3000) for a dispersion dispersed for 30 minutes or more. Went. Ion exchange water was used as the circulating dispersion medium at the time of measurement, and the refractive index of the dispersion was 1.53. The median diameter (μm) was calculated from the particle size distribution on the basis of the volume obtained by the measurement, and was defined as the water-swelled particle diameter.
（４）水膨潤粒子径が１５０μｍ以上の粒子量の測定（湿式ふるい残渣法）
ＪＩＳ Ｋ ００６９−１９９２（化学製品のふるい分け試験方法）に準拠して測定した。
固形分として５０ｇに相当するサンプルを計り取り、同量のエタノールを加えて良くほぐした後、３．０ｌのイオン交換水に、攪拌下ゆっくり注ぎ、３０分間攪拌してサンプルの水膨潤分散液を調整する。次いで、均一分散していることを確認した後、分散液を径７０ｍｍ、目開き１５０μｍの篩に注いで通過させ、ふるい上の残渣を篩からこぼれないように注意して十分な量の水で洗う。次いで、測定後の篩を、通風乾燥機１５０℃、３０分で乾燥した後、デシケータ内で放冷し、乾燥後のふるい重量（ふるい＋残渣重量）を測定する。
下記式により計算される、湿式ふるい残渣（％）を水膨潤粒子径が１５０μｍ以上の粒子量とした。上記以外の操作はＪＩＳ Ｋ ００６９−１９９２（化学製品のふるい分け試験方法）に準拠した。
(4) Measurement of the amount of particles having a water-swelled particle diameter of 150 μm or more (wet sieving residue method)
The measurement was performed in accordance with JIS K 0069-1992 (chemical product screening test method).
A sample corresponding to 50 g as a solid content is weighed, and the same amount of ethanol is added to loosen well, then slowly poured into 3.0 liters of ion exchange water with stirring, and stirred for 30 minutes to obtain a water-swelled dispersion of the sample. adjust. Next, after confirming that it is uniformly dispersed, the dispersion is poured through a sieve having a diameter of 70 mm and an opening of 150 μm, and the residue on the sieve is carefully spilled with a sufficient amount of water so as not to spill from the sieve. wash. Next, the sieve after measurement is dried at 150 ° C. for 30 minutes in a ventilation dryer, and then allowed to cool in a desiccator, and the sieve weight after drying (ie, sieve + residue weight) is measured.
The wet sieve residue (%) calculated by the following formula was used as the amount of particles having a water-swelled particle size of 150 μm or more. Operations other than those described above were in accordance with JIS K 0069-1992 (chemical product screening test method).
以上の結果より、本発明の製造方法は、重合反応に伴う反応器内壁への樹脂付着もなく、また、重合スラリーの濾過性も良好であるので、粒子径の揃った重合体微粒子を生産性よく、粒子同士の凝集もなく製造できることがわかった。これに対して従来技術である比較例１および２は、生産性が悪く、特に実機レベルでは、粒子径の揃った重合体微粒子を生産できないことがわかった。 From the above results, the production method of the present invention has no resin adhesion to the inner wall of the reactor accompanying the polymerization reaction, and the filterability of the polymerization slurry is good. Well, it was found that it can be produced without aggregation of particles. On the other hand, it was found that Comparative Examples 1 and 2 as the prior art had poor productivity, and in particular, polymer fine particles having a uniform particle diameter could not be produced at the actual machine level.
本発明の製造方法によれば、従来の方法と比較して格段に重合体微粒子の粒径が揃った、高品質の球状の親水性の重合体微粒子を、極めて高い分散安定性、重合安定性を維持しながら、重合時や重合後に重合体粒子の凝集、塊化、重合装置への付着などを生ずることなく生産性良く製造することができる。そして、本発明の製造方法では、多官能ビニル系単量体を多量に用いて架橋度の高い親水性架橋重合体微粒子を製造する場合であっても、重合体粒子の凝集、塊化、重合装置への付着などを生ずることなく、粒径の揃った高品質の親水性架橋重合体微粒子を生産性よく製造することができる。 According to the production method of the present invention, high-quality spherical hydrophilic polymer fine particles having extremely uniform particle diameters of polymer fine particles compared with conventional methods are obtained with extremely high dispersion stability and polymerization stability. Thus, the polymer particles can be produced with high productivity without causing aggregation or agglomeration of the polymer particles or adhesion to the polymerization apparatus during or after the polymerization. And, in the production method of the present invention, even when hydrophilic crosslinked polymer fine particles having a high degree of crosslinking are produced using a large amount of polyfunctional vinyl monomer, the polymer particles are aggregated, agglomerated and polymerized. High-quality hydrophilic crosslinked polymer fine particles having a uniform particle size can be produced with high productivity without causing adhesion to the apparatus.
１ ビュレット
２ ピンチコック
３ シリコーンチューブ
４ ポリテトラフルオロエチレンチューブ
５ ロート
６ 試料（重合体微粒子）
７ 試料（重合体微粒子）固定用濾紙
８ 支柱円筒
９ 粘着テープ
１０ 装置用濾紙
１１ 蓋
１２ イオン交換水
1
7 Sample (polymer fine particle) filter paper 8 Fixing column 9
Claims (8)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008022278A JP5509525B2 (en) | 2008-02-01 | 2008-02-01 | Method for producing polymer fine particles |
| US12/865,028 US8362166B2 (en) | 2008-02-01 | 2009-01-20 | Process for the production of polymer microparticles |
| PCT/JP2009/050758 WO2009096266A1 (en) | 2008-02-01 | 2009-01-20 | Process for the production of polymer microparticles |
| EP09705112.2A EP2239277B1 (en) | 2008-02-01 | 2009-01-20 | Process for the production of polymer microparticles |
| PL09705112T PL2239277T3 (en) | 2008-02-01 | 2009-01-20 | Process for the production of polymer microparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008022278A JP5509525B2 (en) | 2008-02-01 | 2008-02-01 | Method for producing polymer fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009179767A JP2009179767A (en) | 2009-08-13 |
| JP5509525B2 true JP5509525B2 (en) | 2014-06-04 |
Family
ID=40912619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008022278A Active JP5509525B2 (en) | 2008-02-01 | 2008-02-01 | Method for producing polymer fine particles |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8362166B2 (en) |
| EP (1) | EP2239277B1 (en) |
| JP (1) | JP5509525B2 (en) |
| PL (1) | PL2239277T3 (en) |
| WO (1) | WO2009096266A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5256590B2 (en) * | 2006-08-04 | 2013-08-07 | 東亞合成株式会社 | Method for producing polymer fine particles |
| JP5251886B2 (en) * | 2008-02-01 | 2013-07-31 | 東亞合成株式会社 | Method for producing polymer fine particles |
| JP5660136B2 (en) * | 2010-08-19 | 2015-01-28 | 東亞合成株式会社 | Drying shrinkage reducing agent for ceramic molding and method for reducing drying shrinkage of ceramic molded body |
| US9302248B2 (en) | 2013-04-10 | 2016-04-05 | Evonik Corporation | Particulate superabsorbent polymer composition having improved stability |
| US9375507B2 (en) | 2013-04-10 | 2016-06-28 | Evonik Corporation | Particulate superabsorbent polymer composition having improved stability |
| US10454111B2 (en) * | 2014-06-10 | 2019-10-22 | Toagosei Co., Ltd. | Electrode for nonaqueous electrolyte secondary battery, method of manufacturing same, and nonaqueous electrolyte secondary battery |
| JP7271962B2 (en) * | 2019-01-22 | 2023-05-12 | 東亞合成株式会社 | Method for producing water-soluble polymer |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US37021A (en) * | 1862-11-25 | Improvement in hose-couplings | ||
| US624967A (en) * | 1899-05-16 | Harrow | ||
| US744564A (en) * | 1903-07-07 | 1903-11-17 | Robert C Kisling | Spring-band. |
| EP0516925B1 (en) * | 1991-03-19 | 1998-05-06 | The Dow Chemical Company | Wrinkled absorbent particles of high effective surface area having fast absorption rate |
| US5216070A (en) * | 1991-09-16 | 1993-06-01 | Isp Investments Inc. | Inverse emulsion crosslinked polyacrylic acid of controlled pH |
| JP3120887B2 (en) | 1992-02-12 | 2000-12-25 | 花王株式会社 | Method for producing water-absorbing polymer fine particles |
| JP3597597B2 (en) * | 1994-06-08 | 2004-12-08 | 株式会社日本触媒 | Water-absorbing resin and method for producing the same |
| US5624967A (en) * | 1994-06-08 | 1997-04-29 | Nippon Shokubai Co., Ltd. | Water-absorbing resin and process for producing same |
| US6323250B1 (en) * | 1999-11-18 | 2001-11-27 | Nippon Shokubai Co. Ltd | Method for production of porous material |
| JP3708901B2 (en) | 2001-05-16 | 2005-10-19 | 花王株式会社 | Silicone-modified water-absorbing polymer particles and production method thereof |
| JP4071030B2 (en) | 2002-04-11 | 2008-04-02 | 花王株式会社 | Surface hydrophobized water-absorbing polymer particles |
| JP4540094B2 (en) | 2003-02-12 | 2010-09-08 | 東亞合成株式会社 | Method for producing porous ceramic |
| DE10338447A1 (en) * | 2003-08-21 | 2005-03-31 | Basf Ag | Use of 2-hydroxy-2-sulfinatoacetic acid or its salts as initiator in W / O emulsions |
| JP5256590B2 (en) * | 2006-08-04 | 2013-08-07 | 東亞合成株式会社 | Method for producing polymer fine particles |
| JP5251886B2 (en) * | 2008-02-01 | 2013-07-31 | 東亞合成株式会社 | Method for producing polymer fine particles |
-
2008
- 2008-02-01 JP JP2008022278A patent/JP5509525B2/en active Active
-
2009
- 2009-01-20 PL PL09705112T patent/PL2239277T3/en unknown
- 2009-01-20 EP EP09705112.2A patent/EP2239277B1/en active Active
- 2009-01-20 WO PCT/JP2009/050758 patent/WO2009096266A1/en active Application Filing
- 2009-01-20 US US12/865,028 patent/US8362166B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009179767A (en) | 2009-08-13 |
| EP2239277B1 (en) | 2013-05-22 |
| EP2239277A4 (en) | 2011-10-26 |
| US8362166B2 (en) | 2013-01-29 |
| WO2009096266A1 (en) | 2009-08-06 |
| US20110040060A1 (en) | 2011-02-17 |
| PL2239277T3 (en) | 2013-10-31 |
| EP2239277A1 (en) | 2010-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5499711B2 (en) | Method for producing polymer fine particles | |
| JP5256590B2 (en) | Method for producing polymer fine particles | |
| JP5509525B2 (en) | Method for producing polymer fine particles | |
| JP5251886B2 (en) | Method for producing polymer fine particles | |
| JP5499712B2 (en) | Method for producing polymer fine particles | |
| JP5273311B2 (en) | Additive for ceramic molding | |
| JP5703567B2 (en) | Method for producing crosslinked polymer fine particles | |
| JP5298547B2 (en) | Method for producing polymer fine particle powder | |
| JP5660136B2 (en) | Drying shrinkage reducing agent for ceramic molding and method for reducing drying shrinkage of ceramic molded body | |
| JP5660135B2 (en) | Drying shrinkage reducing agent for ceramic molding and method for reducing drying shrinkage of ceramic molded body | |
| JP2017113709A (en) | Surfactant carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100708 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130319 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130510 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140225 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140310 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5509525 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |